Microbiological fire-fighting formulation

ABSTRACT

An improved microbiological fire-fighting foam which comprises a bioremediating component, surfactants, foaming agents, and inorganic nutrients, the bioremediating component consisting substantially of sporulating bacteria which are tolerant of the surfactants used, the surfactants selected being innocuous to the bioremediating component used both when the microbes are in a spore state and when activated, and the selected surfactants further being biodegradable by the microbes of the microbial solution. Alternative embodiments of the invention include formulations which comprise perfumes and/or preservatives in addition to the constituents mentioned above. The improved formulation enables microbiological digestion to inert volatile organic compounds and hydrocarbons which may indeed be ablaze when applied.

This is a Continuation-In-Part application of prior patent applications:Ser. No. 08/372,758, filed Jan. 13, 1995, which is now U.S. Pat. No.5,658,961 and Ser. No. 08/285,935, filed Aug. 4, 1994, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a formulation for both extinguishingfires and for decomposing (bioremediating) difficult waste organicmaterials, including hydrocarbons, responsible for the fire; morespecifically it relates to single product useful for controlling andextinguishing organic fires and for cleaning the residual hydrocarbonwaste spills with a component which biodegrades the residual spillproduct in situ, thereby reducing the need for expensive waste handlingand disposal methods which usually involve the removal and disposal ofthe contaminated soil material.

PRIOR ART

1. DiMaio U.S. Pat. No. 5,225,095

2. Norman et al U.S. Pat. No. 5,133,991

3. Spraker U.S. Pat. No. 4,482,632

4. Spraker U.S. Pat. No. 4,288,545

5. "Bioremediation of Marine Oil Spills", Congress of the UnitedStates--Office of Technology Assessment, S/N 052-003-01240-5.

BACKGROUND OF THE INVENTION

Foaming concentrates have been known and used since before 1940 for useas fire fighting agents, for crop protection and for a variety of otherapplications. Ingredients are added for a variety of reasons, forexample: microbicides are often added to discourage bacterial decay ofthe foam, preservatives are added to impart shelf life stability, otheringredients are sometimes added to lower the freezing point, and/or toalter the viscosity.

For many applications it is desirable to produce a foam which ispersistent for several days. Examples of such applications are astemporary covers for landfills and waste piles, covers for spills ofhazardous materials and crop protection against frost. Because of this,a bactericide is usually added as a preservative to prevent thedecomposition of the foam concentrate by bacteria. Protein hydrolysatesare a constituent found in foam of a prior art formulation, as describedin U.S. Pat. No. 5,225,095 to DiMaio, and also U.S. Pat. No. 5,133,991to Norman et al. Because these hydrolysates are excellent nutrientsources for microbiological life forms, a low level toxicity biocide isusually recommended as an additive to preserve the concentrate. The factthat most foams are susceptible to microbial decomposition provides abasis for the conclusion that the art of fire-fighting foams teachesagainst the inclusion of microbial life forms in their formulations.

Organics-decomposing-microorganisms have been commercially available toclean oil spills from oil tankers and to assist in waste removal fromgrease interceptors in restaurants for some time now. Microbesspecifically engineered for the decomposition of difficult organiccompounds are well known and readily available. For example, SybronChemicals, Inc. manufactures the microbiological strains utilized in oneembodiment of the present invention under U.S. Pat. Nos. 4,482,632 and4,288,545, incorporated herein by reference. The microbiological strainsof the Bacillus species particularly effective in the practice of theinvention in connection with the consumption of volatile organiccompounds are B. subtilis, B. licheniformis, and B. polymyxa.

In addition, the selection of one of the above strains is advantageousbecause these species of Bacillus are not true pathogens as are thespecies B. anthracis and B. cereus. Reports of infections in man causedby Bacillus species other than B. anthracis and B. cereus are rare.According to a report by the Department of Biology of the VirginiaPolytechnic Institute and State University, B. subtilis, B.licheniformis, and B. polymyxa as described by the manufacturer, Sybron,would not constitute a public health hazard unless the microorganismswere used in an area where individuals with an unusual vulnerability(such as when undergoing an open-incision surgical procedure) would beexposed.

Investigation of microbial degradation of oil dates back to at least1942, when the American Petroleum Institute began to subsidize researchin the field. Considerable basic knowledge about factors that affectnatural biodegradation, about the kinds of hydrocarbons capable of beingdegraded, and about the species and distribution of the microorganismsinvolved in biodegradation had already been developed in the early1970s. For instance, the Office of Naval Research sponsored more than adozen basic and applied research projects in the late 1960s and early1970s on oil biodegradation to control marine oil spills. Since thistime, a large number of refineries, tank farms, and transfer stationsnow employ in situ bioremediation to restore land contaminated byaccidental spills of fuel oil or other hydrocarbons.

Probably the most important series of field tests of the use offire-fighting foam to control organics and hydrocarbon fires wereconducted in the aftermath of the Persian Gulf War. The oil field firescreated an environment of urgency and necessity which focused creativeminds on solving the problems at hand, and on concentrating on researchand development to solve the problems which were anticipated to occuragain in the future.

LIGHT WATER, Aqueous Film Forming Foam (a product of Minnesota Miningand Manufacturing) is the most commonly used fire-fighting aqueous filmforming foam (AFFF) currently on the market. Despite this fact, it wasrarely used during the oil field fires of Kuwait because of its relativeineffectiveness in extinguishing fires of such a magnitude and intensity(unless the source is completely blanketed with foam) and because of itsrelative inability to prevent flashbacks. In addition, LIGHT WATER andother brands of AFFF contain fluorinated surfactants and butyl-ether,both generally considered to be toxic substances. It has been observedthat some soils contaminated with AFFF several years earlier still foamup during a rain for example. This is evidence of the persistence of thefluorosurfactant used and its resistance to biodegradation. This maypresent a hazard to fish and other forms of wildlife in shallow watersthat breath through their pores, at least until the surfactant used inAFFF is sufficiently diluted or is naturally biodegraded. Being wellaware of these negative side effects to AFFF's use, the United StatesDefense Department has been seeking a non-toxic yet effectivealternative to AFFF.

Microorganisms (microbes) of the type used in the present invention arecapable of assimilating and breaking down the non-soluble organicmaterials including hydrocarbons that compose grease and oil intorelatively harmless substances of water-soluble products, carbon dioxideand a lesser quantity of fatty acids. These types of microorganisms arerelatively commonplace in the environment.

The difficulty encountered in incorporating microbe cultures in afire-fighting foam solution which will extinguish organically fueledfires and begin the disposal of the residual hydrocarbon waste productswere many. The first challenge was the selection of a hardy strain oforganics-consuming (primarily hydrocarbon-consuming) microorganismswhich withstand the extremely severe environment associated withorganically fueled fires in a proportion sufficient to adequatelyaddress the magnitude of the overall bioremediation challenge presented.A second challenge was determining the specific organism that digest ordecompose a particular grease or oil and yet remain capable of beingstabilized so that they have a satisfactory shelf life thereby beingavailable when needed. A third challenge was the selection of amicrobial strain which would stabilize in a surfactant strong enough toextinguish the fire. A fourth challenge was to control the microbepopulation so that they multiply and exist in sufficient quantities soas to accomplish the job of hydrocarbon waste removal in a timelyfashion.

A need therefore exists for a bioremediating fire-fighting foam mixtureand a method for the decomposition of organic materials which meets thechallenges presented in order to reduce cleanup costs and increase thequality of the cleanup by providing an effective and environmentallysafe means to do so.

SUMMARY OF THE INVENTION

The present invention is a formulation of an aqueous mixture ofpreselected microorganisms, inorganic nutrients, a stabilizer, anoptional preservative, foaming agents and surfactants useful forextinguishing fires and bioremediating a fire site. Micro-organisms inthis mixture are stabilized until used and then activated when appliedto waste organic compounds including hydrocarbons. The selection ofspecific activatable microbes, microbe cultures, microorganisms,bacteria, spores, or sporogenous microbe strains will vary depending onthe waste material to be remediated, but is well within the ability ofone of ordinary skill in the art. The presence of the inorganicnutrients solution within the bioremediating component promotes anincrease in the growth and reproductive capacity of the microbes whilefeeding on the material being decomposed. The result of increasedmicrobe growth and reproductive capacity is a greatly increased microbepopulation available to decompose waste organic compounds includinghydrocarbons soon after application, and the sustaining of thismicrobial activity.

In broad practice, this invention comprises a bioremediating componentincluding inorganic nutrients, and a fire-extinguishing componentincluding a foaming agent. The inorganic nutrients in the inorganicnutrients solution support the reproduction and growth of the microbestrains of the bioremediating component. They support the growth andreproduction of these strains when they are activated in the presence ofwaste organic compounds and water. The mixture contains from about 40%to about 50% by volume of an aqueous inorganic nutrients solution, fromabout 30% to about 40% by volume foaming agent and from about 16% toabout 20% by volume of pre-mixed microbe-surfactant solution. Thepreferred embodiment of this invention contains about 45% by volume ofthe inorganic nutrients solution, about 36.7% by volume foaming agent(e.g. ammonium lauryl sulfate), and about 18.3% by volume of thepre-mixed microbe-surfactant solution. The pre-mixed microbe-surfactantsolution itself contains surfactants to disperse and extinguish the fireand facilitate the decomposition of the volatile organic compounds bythe microbe cultures, a stabilizer, a preservative, an optional perfumeor deodorant with the microorganism culture (microbes).

The present invention is a formulation which will not only put out thefire, but go after what caused the fire through microbial decompositionof the most volatile organic wastes, particularly those of hydrocarbonfires. The end product of this decomposition is carbon dioxide,non-toxic water soluble products, and new microbial biomass. The presentinvention has undergone extensive testing at Tyndall Air Force base,Panama City, Fla. and at the Brayton Fire Field at Texas A&M University.It has been found that the microbes of the bioremediating component ofthe present invention are effective in remediating fluorinatedsurfactants, such as found in AFFF formulations.

The motivation for developing a formulation which included microbes forextinguishing fires was founded on an appreciation for the severeenvironmental impact the oil field fires and spills were having on thesoil in Kuwait in the aftermath of the Persian Gulf War. The inventorsought to determine whether a particularly hardy strain of bacteriawould be able to withstand the heat of a fire site immediately afterextinction of a hydrocarbon fire for the purpose of determining how soonafter the conventional extinction of the flame a bioremediating solutioncould be applied and still survive in sufficient numbers to performtheir function. Because of the time for emergency response wherefire-fighting equipment is readily available is typically a shortperiod, and because the procedure for testing the effectiveness offire-fighting foams involves application after only thirty (30) secondsfrom ignition, the temperatures which microbes would be subjected to arequite low--there was little or no concern that the microbe populationwould be severely curtailed when subjected to this relatively low levelof heat. Later tests confirmed this belief--when subjected to "30second" blaze tests, microbe survivability after extinction of theflames was as high as 66 percent. However, in Kuwait, where fires ragedfor several days before extinction, temperatures of the fire siteimmediately after the extinction of the flames were substantiallyhigher, as high as 1800 degrees Fahrenheit in some instances. Inaddition, the ordinary ground temperatures in Kuwait average about 120degrees Fahrenheit.

Recognizing the duty to help remediate the ecological catastrophe inprogress in Kuwait, and the unique opportunity to conduct experiments inthe severest of all earthly environments, trials using a spill-controlformulation comparable to that of the present invention were commencedwith rather surprising results. Not only did approximately thirty three(33) percent of the microbes of the formulation survive the intenseheat, but the formulation extinguished the fire within a period of timewhich indicated that the formulation might be effective as afire-fighting agent, despite the fact that no foaming agents werepresent in the formulation at this time. Again, this was an unexpectedresult--the goal of the application was merely to determine how soon thebioremediating agents could be applied to begin to decompose the organiccompounds. Early analysis of the constituents of the formulation showedthat the manufacturer of a proprietary constituent had permitted someresidual alcohol to remain in the formulation. Alcohol of course is acombustible and its presence was not beneficial to the goal ofextinguishing the flames. The alcohol was subsequently removed from theproprietary constituent with the result being improved fire-fightingcharacteristics of the formulation. It was also observed that the heatof the fire site shortly after the extinction of the blaze caused thesporogenous microbes to come out of spore and begin the work ofdecomposing the waste in a foreshortened period of time.

It should be emphasized that the microbes in the formulation do not helpextinguish the fire--the surfactant contained in the fire extinguishingcomponent of the formulation actually extinguishes the flames and coolsthe surface of the organic waste (oil, the crude and the sludge)sufficiently to permit one-third of the bacteria applied to survive.Ordinary procedure in extinguishing fires is to overspray and tocontinue to apply the foam for at least one minute after the flames areextinguished. It is at this point that most of the surviving microbesare injected into the hazard. The surfactants in the formulation breakdown the volatiles, thereby preventing flashback or re-ignition. It doesthis in part by dispersing the volatile materials through the reductionof its surface tension and subsequent encapsulation of each disperseddroplet of the organic compounds by surfactant molecules. In addition,in the period of time beginning immediately upon application andextinction of the flames, it is the surfactant containing component andnot microbial decomposition which prevents the flash-back through amechanism which breaks down the compounds, changing the molecularstructure of some of the most volatile compounds such that the flashpoint is greatly reduced. The microbes of the present invention thentake over, going to the source of the problem--namely the volatilehydrocarbon or organic compounds which cause the fire. After extinctionof the flames, the presence of the surfactant continues to have asynergistic effect by aiding in the biodegradation process by cleaningaway and dispersing the oil particles so that more surface area isexposed to organics-consuming microbes, thereby speeding the process ofdecomposition. The volatiles are then broken down even further throughmicrobial decomposition such that they no longer constitute an immediatethreat of re-ignition.

The use of the formulation of the present invention also reduces cost asit is no longer necessary to mechanically remove contaminated soil afterthe fire is extinguished--the formulation continues to remediate theproducts of the spill as long as the area is sufficiently moist,breaking the organic material down into carbon dioxide, water-solubleproducts and new biomass.

A key to this invention was the selection of sporogenous microbe strainsmentioned above which (1) stabilizes in a surfactant of sufficientstrength to extinguish the flames and (2) survives the intense heatassociated with such a fire site after extinction of the flames suchthat a significant population of the microbes are present and activatedto begin the decomposition of the volatiles.

The primary goal of the present invention is not to cover (blanket) thecombusting organics (as is common with traditional fire-fighting foams)but rather to penetrate them. Foam is desirable as a medium to help getthrough the heat due to its insulating characteristics, therebyprotecting the bacteria, and as a medium to transport the surfactant andthe microbes to the source of the fire. The foam acts as an effectivecarrier for the microbes and the surfactant solution such that when itcovers an area, the surfactant contained therein is able to drop out ofthe foam directly onto the combusting surface of the organic compounds,thereby extinguishing the flames. Subsequent to the extinction of theflames, the activated microbes drop out of the foam and onto thevolatiles immediately commencing the decomposition process--the microbescome out of spore and begin to attack the source of the fire, convertingit into carbon dioxide, water-soluble products and microbial biomass.

Because of the beneficial effects of foam cited above, ammonium laurylsulfate (ALS) is added as a constituent to aid in the formation of foam.It should be understood that it will be readily apparent to those ofordinary skill in the art to use substitute foaming agents, in place ofor in addition to ALS. However, ALS has been chosen for itseffectiveness as well as its non-toxicity as is evident from itsprevalent use in personal hygiene products such as shampoos.Environmental friendliness is one of the most important considerationsof the present invention--its formulation has been determined such thatsubstantially all of the constituents of this product will biodegrade inabout thirty (30) days time, including surfactants and otherconstituents of foaming agents.

An object of the present invention is a fire-fighting formulation havingthe capability to enhance the bioremediation of a fluorinated surfactanteither already present in the environment or to bioremediate fluorinatedsurfactant contained in the formulation itself subsequent to itsapplication to a fire site. A fire site for present purposes is alocation where there is increased risk of a fire or where a fire hasoccurred.

DETAILED DESCRIPTION OF THE INVENTION

Harnessing the power of microbes is hampered by the lack of control overgrowth and reproductive rates. The present invention comprises a mixtureof a stabilized bioremediating component, a foaming agent and aninorganic nutrients solution and its use for fire-fighting and spillremediation purposes. The presence of the inorganic nutrients causesrapid growth and reproduction of the microbes when contacting wastepetroleum products.

According to a first object of this invention there is provided aprocess for extinguishing an organically fueled fire and for treatingwaste organic spill product by applying a combination fire extinguishingand a bioremediating formulation to the fire site. In a firstformulation, a mixture of inorganic nutrients, foaming agent and(commercially available) pre-mixed microbe-surfactant solution isprepared through a process comprising mixing one part microbiologicalfire-fighting formulation with about 10 to about 100 parts of ordinarytap water. The process further comprises applying this mixture insufficient quantity to cover the combusting area using for example, afire truck pumper with a 1.5 inch hose at 90 to 125 psi and an eductor.After the extinction of the flames and inerting the volatiles, the firesite may be cleaned by rinsing down the substrate with ordinary tapwater so that the waste water and decomposing hydrocarbon biomass drainsaway. The presence of surfactant provides the primary fire-extinguishingagent and its selection is such that it is innocuous to the microbesused. The surfactant used is later consumed by the microbe cultureswhich are a constituent of the invention's formulation.

According to a second object of the invention, there is provided aprocess for treating soil contaminated by waste organic material such asgrease, petroleum or petroleum products which is left behind after anorganically fueled fire has been extinguished.

A third object of the present invention, that of providing an effective,safe and inexpensive means of dealing with fuel or oil fires on publichighways, is explained best by way of the following hypotheticalexample:

An "18 wheeler" tanker spills fuel on the highway which immediatelyignites, and the anticipated time for emergency response is one hour.Adding to this misfortune, the driver has inadvertently collided withanother vehicle in the course of the accident. This second vehicle comesto rest near the flames. Persons are trapped inside. This is a veryhazardous situation--without prior planning, there would be few optionsother than to remain still until the fire department emergency responsepersonnel and equipment arrive. In addition, even if the flames aresomehow extinguished, the possibility remains that until the volatilesare inerted the fuel may re-ignite into flames under little more thanthe weight of a person's foot.

Fortunately, the driver is coherent and is prepared for this eventualityhaving purchased a 2.5 gallon fire extinguisher loaded with MICRO-BLAZEOUT fire-fighting foam (the trade name of a formulation of the presentinvention). He sprays down the contaminated areas--up to 100 square feetwith 2.5 gallons almost immediately extinguishing the flames andsimultaneously beginning the process of inerting the volatilecontaminants.

If the spill in the above hypothetical is comprised primarily of diesel,it will be inerted almost immediately upon contact; if of gasoline, theprocess takes considerably more time--about 5 to 20 minutes depending onthe concentration of gasoline. In either case, this is substantiallyless time than one hour, the time required in this hypothetical for afire truck to arrive. Once the flames are extinguished and the volatilesare inerted, the driver would then be able to help those trapped in thecar and to set up his road blocks, etc.

Again in the above hypothetical, when the emergency response unitarrives, the response personnel need only wash the area off, displacingthe active mixture of contaminates and MICRO-BLAZE OUT fire-fightingfoam to the side of the road. The treated area of the highway becomesnon-skid, because of the cleaning action of the microbe-surfactant mix.The emergency response team can then move that truck off the highway andallow traffic to flow. The material washed to the side of the road maythen be left to digest the residual surfactants and any remainingcontaminants. Of course, it will likely dry up before it completelyremediates the spill. However, the selection of the bacteria is suchthat about 80% of the microbes will survive and go back into spore,remaining idle in this resting state. When the ground is moistened onceagain (e.g. it rains) and the food source is still present, the microbeswill come out of spore and continue to bioremediate the spill until thefood source (the spill product) is completely digested or until the areadries out again. If the area is kept wet, the microbes would likelyconsume a large percentage of the remaining organic compounds in thenext two week period. This will vary of course, depending on the sizeand type of the contaminant.

The microbiological strains mentioned above are selected because oftheir hardiness in that they will stabilize in a surfactant which iscapable of extinguishing a typical organically fueled fire, the factthat they are sporogenous, and have an ability to decompose both thesurfactant used and a particular type of waste found in the typicalhydrocarbon spill. The concentrated mixture contains about 50 to 60billion microbes per quart. The proportion of each microbiologicalstrain in the bioremediating component may be varied according to thecomposition of organic materials to which the solution is applied. Asthe microbes of a particular microbiological strain attack and decomposea component of the spill, those microbes grow and reproduce. If aparticular component is not present in the spill, the microbiologicalstrain that feeds on that component will die out.

In one embodiment of the present invention a pre-mixedmicrobe-surfactant solution is formed when a surfactant and, accordingto need, a stabilizer, a preservative and a perfume are added to themicrobial strains to assist in the decomposition of organic matter andcleanup of hydrocarbon waste. As used herein, the term "pre-mixedmicrobe-surfactant solution" refers to commercially available aqueousmicroorganism culture concentrates, the component's form prior to mixingwith the foaming agent and inorganic nutrients solution. Theconcentrations of constituents in the present invention are derived froma most preferred embodiment which is formulated using BI-CHEM GC600L 6X(Sybron, Inc., Salem, N.J.) as the source for microbes, surfactant,stabilizer, and preservative.

The pre-mixed microbe-surfactant solution of this invention includesabout 54% to about 66% aqueous bacteria culture, up to about 1.7%stabilizer, from about 17% to 21% surfactant, and up to about 2%preservative, the balance being water. The microbial strains present inthe aqueous bacteria culture were selected because they are capable ofdecomposing the organic matter found in grease and waste petroleumproducts. The stabilizer is usually present to maintain the microbepopulation substantially constant until the microbe solution is broughtinto contact with waste organic compounds which act as food for themicroorganisms. The preservatives prevent destruction of the bacteriaculture by toxic organisms. The surfactant acts as the primaryfire-extinguishing agent, the initial inerting agent, as a dispersant,and as a cleaning agent and is an important ingredient of thisinvention. Because of the requirement that it coexist with sporogenousbacteria in either a spore state or in an active state, the surfactantmust be innocuous to the organics-consuming bacteria cultures used. Thesurfactants specifically identified in this specification are allsubstantially innocuous to the microbes selected.

A surfactant by definition is a substance which alters the surfacetension of water, and there are traditionally three types: nonionic,anionic, and cationic. A fourth type which under certain conditions maybe anionic or cationic is known as amphoteric. It is the nature of asurfactant molecule to have one end which is hydrophilic and the otherhydrophobic. While those skilled in the art may determine specificexamples of various surfactants useful in any of the above classes, thepreferred class of surfactants for the practice of this invention is thenonionic surfactant, or a mixture thereof, because it has been found tobe an effective fire-extinguishing agent, to be innocuous to theorganics-consuming bacteria used in the formulation of this invention,and because it is also consumed by the organics-consuming microbes overa reasonable period of time.

Specific examples of nonionic surfactants are compounds which are formedby reacting alkylphenols, particularly octyl- or nonylphenols, withethylene oxide. Those in common use include Triton series (Union CarbideCorporation), the Igepal series (Phone-Poulenc Corporation), the DeSonicseries (Witco Corporation), the Hyonic series (Henkel Corporation), allthose of the chemical class ethoxylated alkyl phenol, the Glucoponseries (Henkel Corporation) and all those of the chemical classpolysaccharide ether. Specific examples include DeSonic 4N, TritonX-100, Igepal Co-630, Igepal Co-730, Hyonic NP-90, Glucopon 225,Glucopon 425 and Glucopon 625. The average number of ethylene oxidemolecules attached to each molecule of alkylphenol is between 1 and 12per molecule of octyl- or nonylphenol. When the ethylene oxide moleculesare between 1 and 4, the surfactant is immiscible in water, whereas ifthe average number of ethylene oxide molecules attached is between 4 and6, the surfactant is dispersible in water, and 7 or above, soluble. Thepreferred nonionic surfactant of those above are those soluble inwater--these surfactants have an average of from 8 to 12 moleculesethylene oxide per molecule of alkylphenol. This includes a surfactantwhich is an alkylphenol and ethlyene oxide derived molecule having atleast 7 to about 15 ethylene oxide moieties per alkylphenol moiety.Other nonionic surfactants may include ethylene oxide adducts of fattyacids, amines or other substances and their derivatives with ethyleneoxide.

Examples of cationic surfactants which may be considered for use in thisinvention are those liquids formed from the quaternary ammonium chloridederivatives of polypropoxy tertiary amines. A specific example ofanionic surfactant which may be useful isoctyphenoxypolyethoxyethylphosphate (a phosphated ethylene oxide adductof octylphenol), a material sold by Rohn and Haas Company (Philadelphia,Pa.) under the trademark TRITON QS-44. This anionic surfactant may be ina free acid form or as an alkali metal salt, preferably the sodium salt.The active ingredient in other anionic surfactants which may be testedfor use in the present invention is sodium. While specific suitable andsuggested possible nonionic, cationic and anionic surfactants have beenset forth, the surfactants which may be used in the present inventionare not limited to those specifically discussed. The foregoingillustrate that water soluble surfactants which are effective at asubstantially neutral pH (from about 5 to about 9) are preferredaccording to the present invention. The selection of the pH is importantto avoid an environment damaging to the maintenance of the viability ofthe microbes. The preferred pH range for the formulation is aboutneutral, i.e. from about 6 to about 8. However, the concentrate willfunction when pH is adjusted within a range of about 4 to 11.5.

Examples of fluorinated surfactants include LODYNE S-15213 (Ciba-GigyCorp., Ardsley, N.Y.) and ZONYL FSA Fluorosurfactant (DuPont Chemical,Wilmington, Del.).

Stabilizers and preservatives added to maintain the microbe populationuntil applied to waste organic compounds are routinely selected bysuppliers of microbes and are not themselves part of this invention. Theselection is within the ability of those of ordinary skill in the art.The presence of stabilizers and preservatives enhances the storage lifeof the invention. An indefinite shelf life has been achieved in theconcentrated mixture based on tests of microbe viability over time.

The most preferred embodiment of the formulation uses pre-mixedmicrobe-surfactant solution GC 600L 6X, (described below), which isunderstood to comprise about 60% by volume aqueous bacteria culture, upto about 1.5% by volume stabilizer, about 19% by volume surfactant, andup to about 2% by volume preservative. The aqueous bacteria culture(bacteria spores in water) comprises B. subtilis, B. licheniformis, andB. polymyxa. A suitable aqueous bacteria culture is supplied by Sybron,Inc. (Salem, N.J.) and is sold under the trade name BI-CHEM SporeConcentrate (P). It contains between 12×10⁷ and 14.2×10⁷ CFU/ml (CFU iscolony forming units). The stabilizer is sodium hydroxide or opacifier(e.g. WITOOPAQUE R-11 from Emulsion Systems); the preservative is amixture of 1,2-benzisothiazolin and dipropylene glycol; and the nonionicsurfactant may be an EO adduct of an alkylphenol such as TRITON X-100(supplied by Rohn & Haas) or NP-9 and NP-13 (supplied by Emery). Perfumemay optionally be added as a deodorizer to improve smell.

The growth and reproductive activity of the microbes is greatly enhancedby the presence of inorganic nutrients. The resulting increase in thequantity of microbes increases the decomposition rate of the organiccompounds thereby neutralizing the threat of re-ignition.

The preferred inorganic nutrients solution useful in the practice of theinvention is made by dissolving water soluble sources of solublenitrogen, phosphorus and potassium mixing from about 0.1% to 0.3% byweight of commercial fertilizer (e.g. 15-30-15 grade SCOTT BRAND) withwater and allowing the mixture to stand until clear, about 21 days andsix hours for this particular fertilizer. It is estimated that theresulting inorganic nutrient solution contains about 0.02% by weight andabout 0.06% by weight nitrogen, between about 0.05% by weight and 0.09%by weight phosphorus, between about 0.02% by weight and about 0.06% byweight potassium with the rest being water and soluble filler material.

Although commercial fertilizer is the preferred source of ingredientsused in the preparation of the inorganic nutrients solution, naturalsources of nitrogen such as found in animal droppings or manure may alsobe used. Some alternative sources of nitrogen, phosphorus and potassiuminclude the various water soluble salts of these components. Thepresence of iron may also have a beneficial effect.

A preferred inorganic nutrients solution is made by mixing about 20pounds of a readily available commercially prepared fertilizer (15-30-15Scott's delayed action lawn fertilizer) and about 8,330 pounds of water.The fertilizer is allowed to stand in the water for about 21 days and 6hours until dissolved. In the preferred embodiment of this invention thefertilizer is placed in a screen holder and lowered into an opening atthe top of a 1,000 gallon tank. Tap water is run over the fertilizeruntil the 1,000 gallon tank is filled. The fertilizer is allowed tostand in the water between 10 to 28 days. In the most preferredembodiment of this invention the fertilizer is allowed to stand in thewater for about 21 days and 6 hours until dissolved. Although longer orshorter periods of digestion may be satisfactory it has been found thatthe solution which has been allowed to stand for 21 days and 6 hoursprovided the most optimum stimulation to active growth and reproductionof microbes as observed under microscopes. The inorganic nutrientssolution made by this process comprises from about 0.1% to 0.3% byweight of a solution of nitrogen, phosphorus and potassium in water.

A preferred formulation of the present invention which is particularlyformulated for forest and/or brush fires and commercial or residentialbuilding fires, comprises approximately 55 parts GC600L 6X (thecomposition of which is described above), 110 parts ammonium laurylsulfate and 135 parts water or, preferably, an aqueous solutioncomprising nutrients such as nitrogen, phosphorous, and/or potassium.The concentrate thus formed remains stable in storage indefinitely and,when premixed with 97 to 99 parts of water (a 1% to 3% soln), producesan effective fire-fighting agent which may be sprayed directly on thefire using for example, a 1.5 inch hose at 90 to 120 psi. Alternatively,the formulation may be applied using an eductor, a mechanism used topull the concentrate material into the water stream from a concentratecontainer. The formulation has been observed to extinguish the flames oncontact without substantial danger of flash-back.

A preferred formulation for the present invention which is particularlyformulated for crude oil fires, comprises approximately 55 parts, 110parts ammonium lauryl sulfate and 135 parts of an aqueous solutioncomprising inorganic nutrients such as nitrogen, phosphorous, andpotassium. The concentrate thus formed remains stable in storage for atleast 12 months and, when diluted with 94 to 97 parts by volume of water(a 3% to 6% soln), produces an effective fire-fighting agent which maybe sprayed directly on the fire using for example, a 1.5 inch hose at 90to 120 psi (note: it is contemplated that the injection of air into themix immediately before application will enhance foam production suchthat the percentage of ALS in the formulation may be substantiallyreduced). The formulation has been observed to extinguish the flames oncontact without substantial danger of flash-back.

On a volumetric basis, a formulation of the present invention relates toa microbiological fire-fighting formulation of inorganic nutrients,foaming agent and bioremediating component comprising about 45% byvolume of inorganic nutrients solution, about 36.7% by volume foamingagent (e.g. ALS) and about 18.3% by volume pre-mixed microbe-surfactantsolution (e.g. GC600L 6X), wherein the pre-mixed microbe-surfactantsolution comprises a surfactant, a stabilizer, a preservative and amicroorganism culture. After mixing the inorganic nutrients solution,the foaming agent and the pre-mixed microbe-surfactant solution in theamounts as disclosed above, the mixture comprises about 9% to about 12%by volume bacteria culture, up to about 0.28% by volume stabilizer,about 3% to about 5% by volume surfactant, and from 30% up to about 36%by volume foaming agent. Of course, trace amounts of the nutrients ofthe inorganic nutrients solution are also present in the mixture. Theinorganic nutrients in the inorganic nutrients solution aresubstantially effective in causing the microbes to double in populationevery twenty minutes. In this formulation of the invention themicrobe-solution comprises a nonionic surfactant, a stabilizer, apreservative and a microorganism culture. In addition, it should benoted that the composition as described above wherein the percentage offoaming agent is reduced to as low as 10% (the deficit being made up byincreasing the volume of bacteria culture) has been tested withsatisfactory though less than optimal results.

According to a preferred and currently practiced formulation of thepresent invention there is provided a microbiological fire-fightingformulation comprising about 18.3% by volume BI-CHEM GC 600L 6X (SybronChemicals, Incorporated), about 36.7% by volume ammonium lauryl sulfate(a foaming agent), and about 45% by volume preferred INORGANIC NUTRIENTSsolution. Normal strength BI-CHEM GC 600L is comprised of 10% by volumeBI-CHEM spore concentrate (P); 3.2% by volume nonionic surfactant suchas TRITON X-100 (by Rohn & Haas), NP-9 or NP-13 (by Emery); 0.25%opacifier spore stabilizer such as WITOOPAQUE R-11 (by Emulsion Systems)or sodium hydroxide; and 0.3% perfume such as 86F/471 (by FragranceResources, Keyport, N.J.), 407322 (by Fragrascent Neumark Extra, byIngredient Tech Corp., Des Plaines, Ill.) or Arylene N. Fragrance (byArlyessence, Inc.), with the balance being water. A preservative mayoptionally be used. GC 600L 6X as used in the present invention is aconcentrate of GC 600L (6 times normal concentration) and is readilyavailable on the market. However, in the formulations of the presentinvention, a trace amount of alcohol which is normally a constituent inthe commercially available product is removed by the manufacturer byrequest prior to use in the present invention.

The ALS used in the formulation of this invention is comprised of about30% to 33% ammonium lauryl sulfate solution having a specific gravity of1.05 at 25 degrees C.

Opacifier present in GC600L 6X is a stabilizer which helps ensure thatthe microbes remain in spore while in storage and until applied to theorganic compounds to be consumed. When diluted with water or inorganicnutrients solution, the concentration of stabilizer remains sufficientto keep the microbes in spore until a food source is available. When themicrobes are excited by the presence of a food source, they then becomeactivated and are able to begin the decomposition of organic wastes.

The perfume used in the currently practiced formulation of the presentinvention is of course optional. It has been found that the pleasantmasking odor of the perfume helps in improving the working environmentaround a spill for the emergency response personnel.

As taught above, the present invention may be practiced using anysuitable surfactant, including a fluorinated surfactant containingfire-fighting component such as may be found in AFFF. In fact, AFFF hasbeen successfully used as an ingredient of the present formulation.Formulations of the present invention using a fluorinated surfactantsincludes:

1. 1 gallon UNIVERSAL PLUS (National Foam, Inc., Exton, Pa.) to 5gallons of the present formulation.

2. 1 gallon UNIVERSAL GOLD (National Foam, Inc., Exton, Pa.) to 5gallons of the present formulation

3. 1 gallon LODYNES-15213 (3% by volume, Ciba-Gigy Corp., Ardsley, N.Y.)5 gallons of the present formulation.

4. 1 gallon ZONYL FSA Fluorosurfactant (DuPont Chemical, Wilmington,Del.) to 5 of the present formulation.

The resultant stock formulations may be then mixed with water to a finalconcentration of fluorinated surfactant of about 0.1 to 5.0 percent forapplication to a fire. A stock formulation comprising FSA and thepresent formulation diluted with water to a final concentration of 1.0percent FSA and applied to a hydrocarbon fire was very effective inextinguishing the fire.

An additional embodiment of the present invention comprises 1 quartGC600L (Sybron, Inc.) as bioremediating component to 1 gallon LODYNES-15213 (3% by volume, Ciba-Gigy Corp., Ardsley, N.Y.) as thefire-fighting component may be combined to comprise a formulation of thepresent invention.

Another specific formulation of the present invention is:

55 gallons of GC600L 6X;

110 gallons of ALS;

10 pounds polymer;

3 gallons ZONYL FSA Fluorosurfactant (DuPont Chemical, Wilmington,Del.); and

135 gallons water.

Procedure: Combine all materials in the tank of a shearing machine. Letmaterials shear for 30 minutes. Additionally, the mixture may betransfered to and further mixed in a packaging tank until foam andremaining solids are substantially gone.

Polymers as used in the present invention are known in the art offire-fighting formulations and includes various polysaccharidecompositions known to one skilled in the art. An example of one suchpolymer suitable for use in the present invention is KELZAN (KelcoCorp., San Diego). Polymers are used in fire-fighting formulations toemulsify and suspend ingredients and to maintain homogeneity of themixture. In this specific formulation, it is preferred that the polymerused be at least about half (5 pounds) KELZAN.

At the time of application to a fire, the present invention is mixedwith water preferably in the ratio comprising one part by volumeformulation and between 17 parts and 100 parts by volume water,depending on the type of fire to be extinguished. Additionally, thediluted formulation may be turbulated prior to application to the fire.

The following example is given to aid in the practice of this inventionand is for the purposes of illustration only and should not be construedas being limiting on the overall scope of the invention described.

EXAMPLE 1

A representative test comparing the effectiveness of the formulation ofthe present invention with AFFF (3M Company) was conducted at theBrayton Fire Field at Texas A&M University. A 21 foot diameter (346square feet surface area) steel tank is filled with 65 gallons of dieseland 15 gallons of gasoline. The fuel is ignited and allowed to burn for30 seconds prior to an attempt to extinguish the flames. The equipmentused to apply a 3% solution of MICRO BLAZE OUT fire-fighting foamincludes a pressure nozzle set mid-range at a 95 gallons per minute(therefore, 3.6 GPM/square foot) dispense rate using a straight stream.Result is an extinguishment time of 30 seconds.

AFFF testing under the same conditions extinguished the flames in acomparable period of time, but at a product cost 20% greater than theMICRO-BLAZE OUT used. In addition, the use of AFFF raises environmentalconcerns, possibly requiring mechanical removal at considerableadditional expense.

Variations of the formulation used in the Example above can be preparedby altering the relative amounts of ingredients and/or by replacing themwith functionally similar ingredients. Formulations have been preparedwith greater and less amounts of ALS, and inorganic nutrients withacceptable, although not optimal results.

The order of the ingredients added and mixing technique are notparticularly important. However, the typical preparation of theformulation proceeds as follows: first, one fifty-five (55) gallon drumof GC 600L 6X is placed in a three hundred (300) gallon mixingcontainer. To this is added one fifty-five (55) gallon drum of the ALS.Then fifty-five (55) gallons of inorganic nutrients solution is added.Another fifty-five (55) gallon drum of ALS solution is added. Thebalance of the 300 gallon formulation is made up of either water orinorganic nutrients solution. The container is then capped off andmixed. It is then ready to ship. At the site, it may be diluted withwater in an amount depending on the application for which it is to beused. The pH of the formulation remains about neutral, and is rarelyabove 8. It has therefore not been observed to be necessary to controlthe pH of the formulation. However, if pH control is necessary, pH maybe adjusted using NaOH or HCl.

It is contemplated that additives may be used to enhance the bubblestability of the foam. In addition, it is likely that any number ofknown freezing point depressants may be added to the basic formulationto help prevent freezing of the concentrate. The additives used in theformulation of this invention are those which exhibit minimal adverseenvironmental and toxic effects. It is anticipated that theseenvironmentally safe components could be replaced by less desirableagents, if necessary, without substantially diminishing thefunctionality of the invention.

The basic formulation is diluted to a range of from approximately 1% to6% with water prior to turbulation to produce foam. The preferreddilution is dependent on the type of fire, but a relatively wide rangeis functional. At 3% (i.e. 97 parts per hundred volume of water)dilution, the solution produces a quality foam which is highly costeffective.

The advantages of the present invention have been clearly presented. Theformulation of the invention as described above and in the claims belowprovides a fire-fighting foam and residual spill control agent which canbe stored indefinitely and dispensed as required from conventional fireextinguishing devices. The formulation begins to work immediately,extinguishing the fire and breaking down some of the most volatileorganic materials in only a matter of minutes. This enables thestabilization of volatile surfaces in a short period, decreasing theimmediate danger of explosion or ignition and thereby protecting livesand property. This ability is enhanced by the presence of surfactants inthe formulation which begin the process of inerting the volatiles anddisperses the organic compounds such that more surface area is exposedfor microbial decomposition.

Thus it is apparent that in accordance with the present invention, animproved foamable concentrate and method of mixing same is providedwhich fully satisfies the objectives set forth above. While theinvention has been described in conjunction with specific embodiments,it is evident that many alternatives, variations, modifications andpermutations will become apparent to those skilled in the art in lightof the foregoing description. Accordingly, it is intended that thepresent invention embrace all such alternatives, variations,modifications and permutations as fall within the spirit and broad scopeof the appended claims.

What is claimed as new and desired to be secured by Letters Patentis:
 1. A method of using a mixture which comprises an aqueous solutionof:(i.) a fire extinguishing component including a biodegradable foamingagent, and (ii.) a sporogenous bacteria containing bioremediatingcomponent, to bioremediate a fire site where fluorinated surfactants arepresent comprising the steps of:combining said mixture with water toform a dilution having a ratio of about 1 part of said mixture to about10 to 100 parts of water; turbulating the dilution; applying asufficient amount of the dilution over the surface of said fire site tobioremediate the fluorinated surfactants present at said fire site; andleaving the dilution in place on said fire site to bioremediate thefluorinated surfactants present at said fire site.
 2. A method of usinga mixture which comprises an aqueous solution of:(i.) a fireextinguishing component including a biodegradable foaming agent, and(ii.) a sporogenous bacteria containing bioremediating component toextinguish a fire and bioremediate a fire site where fluorinatedsurfactants are present comprising the steps of:combining said mixturewith water to form a dilution having a ratio of about 1 part of saidmixture to about 10 to 100 parts of water; turbulating the dilution;applying a sufficient amount of the dilution over the surface of saidfire site to extinguish and to prevent re-ignition of said fire and tobioremediate the fluorinated surfactants present at said fire site; andleaving the dilution in place on said fire site to bioremediate saidfire site and bioremediate the fluorinated surfactants present at saidfire site.